Acid wool dyestuffs of the anthraquinone series and a process of making same



Patented Aug. 25, 1931 UNITED STATES ACID WOOL mzns'rurrs on THE PATENTOFFICE GnonG-KALIsoHEn, or-FRANKFOR'r-QN THE-MAIN, AND ma 1101mm, or FRANK- FORT-ON-THE-MAIN-FECHENHEIM, GERMANY, Assrenons'ro GENERAL Anrnrnn WORKS, INC., on NEW YORK, N. 'Y., A CORPORATION OF DELAWARE ANTHRAQUINONE SERIES AND A PROCESS OF MAKING SAME No Drawing. Application filed January 29, 1929, Serial No. 336,000, and. in Germany February 1 1928 0 NH? H The connection of the amino-anthraquinone and the benzyl residue by means of a sulfur atom may be elfectedby condensing a benzyl mercaptan with a halogen amino-anthraquinone compound or by condensing a benzyl-halide with an amino-anthraquinone mercaptan compound. The introduction of the sulfonic acid group into the benzyl residue may be carried out before or after forming the thio-ether bond. It generally already occurs at a. low temperature, when using concentrated sulfuric acid. When a benzyl-amino-anthraquinonyl-thioether compound is 'sulfonated, the anthraquinone residue of which contains other easily sulfonizable residues besides the thiobenzyl group, dior poly-sulfonic acids can be obtained, which acids are sometimes of a special value, owing to their higher solubility.

The new dyestuffs obtained according to 'our present process dye different shades varying from yellowish red to greenish blue according to the auxochromic groups present in their molecule. The presence of a sulfonic group in the benzyl residue has an especially favorable influence on the levelling property of the dyestuffs.

In order to further illustrate our invention, the following examples are given, the

parts being y Weight and all temperatures i in centigrade degrees. We wish it however to beunderstood that we are not limited to the particular products, nor reaction conditions mentioned therein.

Example 1 30 parts of 1.4-diamino-2 mercapto-Zw-chloro-anthraquinone are dissolved in 150 parts of alcohol and 12 parts of a caustic soda solution of 40 B. To this solution 15 parts of benzyl-chloride are added. After a short time the new lAc-diamino-3.-chloro-anthraquinone-Q-benzylsulfide separates in a crystal lized-form. It melts at about 208 and corresponds to the formula,

O 17TH:

10 parts of this sulfide are dissolved in parts of sulfuric acid monohydrate and the solution is I gradually warmed to (SO-70, while stirring. After about 3"hours the mass is poured on ice and the separation of the dyestufi' is completed by the addition of com mon salt. probably to the formula ly colorless and becomes dark blue after the addition of paraformaldehyde 7 Example 2 A solution of 27.5 parts of thesodium salt The new dyestuff correspondsof benzyl-chloride-para-sulfonic acid in parts of water is allowed to run into a solution of 30 parts of the sodium salt of lA-diamino-2-mercapto-3 chloro anthraquinone' in 300 parts of water. The mass is stirred at 60 for about 3 hours. Then the dyestuff is precipitated by the additionof common salt. It is identical with that described in Example 1.

Example 3 40 parts of 1.4-diamino-3-chloro-anthraquinone-2-benzylsulfide described in Example l are suspended in 200 parts of alcohol. To this suspension a solution of 50 parts of crystallized sodium sulfide and 7 parts ofsulfur .in 200 parts of water is added and the whole is boiled for somehours. Then the alcohol is distilled ofi and the sodium salt of L l-diamino-3-mercapto anthraquinone- 2 -benzylsulfide is isolated by the addition of common salt. This sodium mercaptide is again dissolved in alcohol and condensed with 15 parts of benzyl-chloride. After a short time 1.4-diamino anthraquinone-2.3-di-benzylsulfide, separates. It melts at .about 197 and corresponds to the formula NHg 30 parts of this disulfi'de'are dissolved in400 parts of sulfuric acid monohydrate and the solution is maintained at'70 for some hours. Then the'mass is poured on ice and the new dyestufi' is isolated by the addition of common salt. It corresponds probably to the formula I I'H: "in water to a blue solution and dyes wool dark blueshades of an excellent It dissolves fastness. nearly colorless and becomes blue when mixed with paraformaldehyde.

Example 8 parts of l.4-diamino 2-phenoxyf3 chloroanthraquinone are treated in'an alcoholic suspens1on with a sodium disulfide solution and thesodium ,mercaptide, thus obtained, is condensed with 'beuzyl-chloride in the man; Thereby 1.4-j

ner described in Example 8. diamino- 2 -phenoxy-anthraquinone- 3 -benzyl ing to the formula 0 i s, I

sulfide melting at about 224 and correspond- Its solutioniin sulfuric acidis is formed. 10 parts of this compound are dissolved in parts of sulfuric acid monohydrate and the solution is maintained at 40 for 2 hours, While stirring. The new dyestuff. is isolated as described in the foregoing examples. It corresponds probably to the formula I o -otrn soiu flS-CHPI-OSOEL i l lHz Its solution in sulfuric' acid is'feebly red and becomes blue, when mixedwith oaraformalde'hyde. The dyestulf dissolves in water to a violet solution and dyes wool fast, violet shades. V i i 20 parts of this 'compound are dissolved in parts of sulfuric acid monohydrate and the solution is heated to 80 for some hours. The new dyestufi is worked up as described in Example 1. It corresponds probably to the formula e l i7 OH:

".soau

Itv dissolves in sulfuric acid to aviolet- $0111; 1 tion tu-rnin bhw ont'he addition of paraformaldehyde.'- The dyestufi dyes Wool greenish blue-grey-s'hades. i

l'Vhe-n 1amino-2emercap'to-L-para-to'lyl-v amino-anthraquinone is replaced, by the correspondingphenyl-ainino compound and the process is otherwise carried out in afl-i-ke manner, a dyestufl is obtained Wh1ch has nearly thesame properties and an analogous, oonstltutlon. f

" 'Emampleb' A solutionof 2' 7.5-parts of th'es'odium salt of benzyl-ch'loride-parasulfonic acid in: '80

1 parts *ofzwater is allowed to run into a solution of 30 parts of thesodium salt of l-amino -2 mercapto 4-paratolylamino :anthra quinone in 800 parts of water. The mixture is stirred at 60 for about 3 hours. Then the new dyestuff is isolated as described above. It corresponds to the formula It dissolves in sulfuric acid toa violet solution and dyes wool bluish grey shades. By further sulfonating this mono-sulfonic acid a dyestulf probably identical to that of EX- ample 5 is obtained.

Example '7 1 amino -2.4- dibromo anthraquinone is condensed with cycloheXyl-amine. The formed l-amino-2-bromoA-cycloheXyl-amino-anthraquinone is treated with sodium polysulfide to prepare l-amino-Q-mercapto-lcyclohexylamino-anthraquinone. This mercaptan is allowed to react with benzyl chloride and the l-amino-4-cyclohexylamino-anthraquinone 2 :benzyl sulfide melting at about 199, thus obtained, is sulfonated in the manner described above. Thereby a new dyestuff is produced which dyes wool bright blue shades. It corresponds to the formula 0 NHn It dissolves in sulfuric acid to a yellowish brown solution.

We claim:

1. A process for the manufacture of anthraquinone thioethers which comprises condensing an anthraquinone mercaptan corresponding to the general formula:

wherein R stands for hydrogen or an aryl or cycloalkyl group, one Y stands for hydrogen, halogen or an ether or thioether group and the other Y for SH, witha benzyl halide, and sulfonating the product thus obtained.

2. A process for the manufacture of anthraquinone thioethers which comprises condensing an anthraquinone mercaptan lcorre-' spondmg to the general formula:

wherein R stands for hydrogen or an aryl or cycloalkyl group, one X stands for the group SCH C H SO H and the other X for hydrogen, halogen or an ether or thioether powders, soluble in water, dyeing wool from an acid bath fast yellowish-red to greenishblue shades and showing an excellent levelling property.

5. As new products acid wool dyestuffs corresponding to the probable general formula:

cycloalkyl group, and X stands for hydrogen, halogen or an ether or thioether group, which products are yellowish-blue powders, soluble in water, dyeing wool from an acid bath fast yellowish-red to greenish-blue shades and showing an excellent levelling property.

6. As a new product the acid wool dyestuff of the probable formula I group, which products are yellowish-blue 5100 wherem R stands for hydrogen or an aryl or which product is abluish Violet powder, sol- Y uble in sulfuric acid'to a nearlycolorless solution becoming dark blue on the addition of para-formaldehyde, soluble in Water to a 5 bluish Violet solution, dyeing Wool from an acid bath fast bluish violet shades and showing an excellent levelling property.

In testimony whereof, We aflix our signatures.

10 GEORG KALISCHER.

ERNST HONOLD.

Certificate of Correction Patent No. 1,820,023. Granted August 25, 1931, to

GEORG KALISCHER ET AL.

It is hereby certified thet error appears in the printed specification of the abovem bered patent requlrlng correctlon as follows: Page 1, immedlately following the formula between lines 13 and 20, insert the expression wherein]? stands for hydrogen or an argl or og oZoaZh z Z group, one X stands for the group S 0H 0 H S0 H and the other X for hydrogen, halogen or an other or thtoother group; and that the said Letters Patent should be read With this correction therein that the same may conform to the record of the case in the Patent Oflice.

Signed and sealed this 24th day of November, A. D. 1931.

[SEAL] M. J. MOORE,

Acting Oommz'ssz'oner of Patents. 

